Diallyl esters of phosphorous acid



reaction mixture of a tertiary Patented Jan- 31, 1950 lTED STATES PATENT OFFlCE 2,495,958 DIALLYL ns'rsas or rnosrmonous ACID w a Craig, Philadelphia, and William F. Hester,

D'rcxel Hill, Pa., assi Company, Philadclp De ware snore hia, Pa. a corporation of to Riihm & Haas No Drawing. Application August 7, 1947, Serial No. 767,316

3 Claims. (61.260461) This invention concerns diesters of allyl or methallyl alcohol and phosphorous acid. These esters are of the structure (CH2=CR'CH2O) zPOH wherein R is hydrogen or the methyl group. They have fungicidal properties which fit them for use in fungicidal preparations for treating plants. They are also useful as intermediates, as, for example, in the preparation of derivatives formed with aldehydes, as described in application Serial No. 620,636, filed October 5, 1945, now

Patent No. 2,485,573.

The diesters of this invention may be prepared by reaction of allyl alcohol or methallyl alcohol with phosphorus. trichloride, presumably to form a triester which reverts to the diester; thus, in the case of allyl alcohol,

Practically, however, the products obtained in such direct reaction with allyl alcohol and methallyl alcohol tend to contain a considerable proportion of the monoester. The yield of the diesters can be much improved by use in the amine which is free of groups reacting with phosphorus trichloride.

of 10 to 60 C.

The preparation of the compounds of this invention is shown in the following illustrative examples.

Example 1 To a stirred mixture of 261 grams of allyl alwas filtered d. The filtrate was concentrated on a boiling water bath to yield 292 grams of a viscous yellow oil. This oil corresponded in composition fairly closely with CH2= CHCHaO) :POH.

Example 2 To a stirred solution of 983 grams of allyl alcohol and 937 milliliters of pyridine in two thousand milliliters of ethylene dichloride, there was added 825 grams of phosphorus trichloride during the course of three hours. The temperature of the reaction mixture was kept below C. by external cooling. After the phosphorus trichloride had been added, the mixture was stirred for two hours and left standing overnight. The pyridine hydrochloride which had separated was was added to the heated on a boiling water bath and the volatile materials removed therefrom under reduced pressure. A small amount of diatomaceous earth atures.

A sample of this product was taken up in acetone and diluted with water to give a 1% solution. This solution was fungicidal as shown by-slide germination tests sarcinaeforme Cav. and A solution diluted to 0.1% concentration was still toxic to M acrosporz'um sarcinaeforme.

Example 3 A mixture was made from 432.6 grams of methallyl alcohol, 316.4

course of almost three hours. The reaction mixture was maintained between 9 and C. It was stirred for an hour and twenty minutes after the trichloride had been added. Pyridine hydrochloride sepreaction mixture water bath under reduced pressure. A clear yellow oil was obtained containing by analysis about 15% of phosphorus and corresponding to the deon a boiling This application is a continuation-in-part of our application Serial No. 620.636, filed October 9,495,958 3 4 5, 1945, wherein the claimed diesters were first mm disclosed.

We claim: The following references are of record in the 1. Compounds of the formula me of this Patent:

cm=c 'cm0),Po 5 UNITED STATES PATENTS wherein R is selected from the class consisting Number Name D9470 of hydrogen and the methyl group. 2,394,829 Whitehill et a1. Feb. 12, 1948 2. A compound of the formula OTHER, REFERENCES (CH2=CHCH2O)2POH 10 hemical Ab tracts," vol. 13 (1919). p les 2865-66, abstract of an article by Mllobendzki A the et a1., Chemik Polskl, vol. 15, 34-7 (1917).

(CHs=C(CI-Is) CHnO) zPOH W E CRAIG. 1|

WIILIAM F. HESTER. 

1. COMPOUNDS OF THE FORMULA 